U.S. patent application number 12/044718 was filed with the patent office on 2009-09-10 for method for enhancing dispersion of inorganic compounds using silicone-containing esters and compositions formed therefrom.
Invention is credited to Wenning Wang Han, Bernie J. Pafford, James Zielinski.
Application Number | 20090226385 12/044718 |
Document ID | / |
Family ID | 40547418 |
Filed Date | 2009-09-10 |
United States Patent
Application |
20090226385 |
Kind Code |
A1 |
Han; Wenning Wang ; et
al. |
September 10, 2009 |
Method for Enhancing Dispersion of Inorganic Compounds Using
Silicone-Containing Esters and Compositions Formed Therefrom
Abstract
A cosmetic composition comprising: (a) an aqueous and/or oil
phase comprising: (i) water, and (ii) at least one cosmetically
active ingredient; (b) a coupling agent; and (c) an oil phase
comprising: (i) an isoparaffin solvent, and (ii) a
silicone-containing solvent having the formula: ##STR00001##
Inventors: |
Han; Wenning Wang;
(Lawrenceville, NJ) ; Zielinski; James; (Somerset,
NJ) ; Pafford; Bernie J.; (Berkeley Heights,
NJ) |
Correspondence
Address: |
EXXONMOBIL CHEMICAL COMPANY
5200 BAYWAY DRIVE, P.O. BOX 2149
BAYTOWN
TX
77522-2149
US
|
Family ID: |
40547418 |
Appl. No.: |
12/044718 |
Filed: |
March 7, 2008 |
Current U.S.
Class: |
424/59 ; 424/65;
514/770 |
Current CPC
Class: |
A61K 8/89 20130101; A61Q
5/02 20130101; A61Q 17/02 20130101; A61Q 17/04 20130101; A61Q
17/005 20130101; A61Q 15/00 20130101; A61Q 5/12 20130101; A61Q
19/001 20130101; A61K 2800/262 20130101; A61K 8/31 20130101; A61Q
19/00 20130101 |
Class at
Publication: |
424/59 ; 514/770;
424/65 |
International
Class: |
A61K 8/25 20060101
A61K008/25; A61K 47/04 20060101 A61K047/04; A61Q 15/00 20060101
A61Q015/00; A61Q 17/00 20060101 A61Q017/00 |
Claims
1. A cosmetic composition comprising: (a) an aqueous phase
comprising: (i) water, and (ii) at least one cosmetically active
ingredient; (b) a coupling agent; and (c) an oil phase comprising:
(i) an isoparaffin solvent, and (ii) a silicone-containing solvent
having the formula: ##STR00068## wherein: R.sup.1 are independently
selected from the group consisting of: an alkyl having 1-5 carbon
atoms, a substituted alkyl having 1-5 carbon atoms optionally
substituted by one or more fluorine atoms, and a phenyl, and
R.sup.2 is selected from the group consisting of: hydrogen, alkyl
of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon atoms
optionally substituted by one or more fluorine atoms, aryl, a
partially esterified ester-containing group represented by the
formula: ##STR00069## and a reverse ester thereof represented by
the formula: ##STR00070## and the formula: ##STR00071## and a
reverse ester thereof represented by the formula: ##STR00072##
provided that if R.sup.1 is anything but methyl or ethyl, then
R.sup.2 must be a methyl, ethyl or butyl, R.sup.3 is derived from a
partially esterified ester residue; R.sup.8 is selected from the
group consisting of: hydrogen, alkyl of 1 to 45 carbon atoms,
substituted alkyl of 1 to 45 carbon atoms optionally substituted by
one or more fluorine atoms, aryl and a compound derived from a
partially esterified ester residue; R.sup.9 is selected from the
group consisting of: an arylene, an alkylene of 1 to 22 carbon
atoms, substituted alkylene of 1 to 22 carbon atoms optionally
substituted by one or more fluorine atoms and arylene; R.sup.4 is
selected from the group consisting of: alkyl of 1 to 45 carbon
atoms, substituted alkyl of 1 to 45 carbon atoms optionally
substituted by one or more fluorine atoms, aryl, said
ester-containing group and said compound derived from reverse
esters thereof, m is an integer between about 5 to about 22; and x
is an integer between about 0 to about 1000; wherein said
composition has at least 1 compound derived from said partially
esterified ester-containing group or said reverse ester
thereof.
2. The composition according to claim 1, wherein said isoparaffin
solvent has a boiling range between about 100 to 340.degree. C.,
wherein said isoparaffin constitutes between about 1 to 75% by
weight, of the total of said oil phase.
3. The composition according to claim 1, further comprising (d) a
silicone-containing surfactant.
4. The composition according to claim 3, wherein said
silicone-containing surfactant is an alkoxylated, alkyl substituted
siloxane surface active agent.
5. The composition according to claim 4, wherein said
silicone-containing surfactant is dimethicone copolyol or a mixture
of dimethicone copolyol and cyclomethicone.
6. The composition according to claim 1, wherein said
silicone-containing surfactant is present in an amount between
about 0.2 to 2% by weight, of the total weight of said
composition.
7. The composition according to claim 1, wherein said coupling
agent is present in an amount between about 10 to 30% by weight, of
the total weight of said composition.
8. The composition according to claim 1, wherein said isoparaffin
solvent is a saturated aliphatic hydrocarbon containing at least
one side chain, and wherein the total carbon atoms are in the range
between about 8 to 20.
9. The composition according to claim 1, wherein said isoparaffin
constitutes between about 25 to 50% by weight, of the total of said
oil phase.
10. The composition according to claim 1, further comprising at
least one additional additive selected from the group consisting
of: emollients, humectants, antiseptics, antioxidants, chelating
agents, ultraviolet absorbers, colorants, fragrances and
preservatives.
11. The composition according to claim 1, wherein said composition
is a deodorant, antiperspirant, sunscreen, insect repellent or
anti-fungal agent.
12. The composition according to claim 1, wherein said composition
exhibits at least one property selected from the group consisting
of: substantially odor-free; a refractive index in the range
between about 1.41_to about.sub.--1.46; solubility parameters in
the range between about.sub.--7_to
about.sub.--9.+-.1.5_'d(i)@25.degree. C. (cal/cc) 1/2; viscosity in
the range between about 35_to about 2450_cSt@25.degree. C.; and
surface tension in the range between about 20 to about
23_dynes/cm.
13. The composition according to claim 1, wherein said composition
is one selected from the group consisting of: sunscreens, shampoos,
lip balms, moisturizing lotions, and antiperspirants.
14. A process for preparing a cosmetic composition comprising
mixing the following: an aqueous phase comprising: (i) water, and
(ii) at least one cosmetically active ingredient; a coupling agent;
an oil phase comprising: (i) an isoparaffin solvent, and (ii) a
silicone-containing solvent having the formula: ##STR00073##
wherein: R.sup.1 are independently selected from the group
consisting of: an alkyl having 1-5 carbon atoms, a substituted
alkyl having 1-5 carbon atoms optionally substituted by one or more
fluorine atoms, and a phenyl, and R.sup.2 is selected from the
group consisting of: hydrogen, alkyl of 1 to 45 carbon atoms,
substituted alkyl of 1 to 45 carbon atoms optionally substituted by
one or more fluorine atoms, aryl, a partially esterified
ester-containing group represented by the formula: ##STR00074## and
a reverse ester thereof represented by the formula: ##STR00075##
and the formula: ##STR00076## and a reverse ester thereof
represented by the formula: ##STR00077## provided that if R.sup.1
is anything but methyl or ethyl, then R.sup.2 must be a methyl,
ethyl or butyl, R.sup.3 is derived from a partially esterified
ester residue; R.sup.8 is selected from the group consisting of:
hydrogen, alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to
45 carbon atoms optionally substituted by one or more fluorine
atoms, aryl and a compound derived from a partially esterified
ester residue; R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene; R.sup.4 is selected from the group
consisting of: alkyl of 1 to 45 carbon atoms, substituted alkyl of
1 to 45 carbon atoms optionally substituted by one or more fluorine
atoms, aryl, said ester-containing group and said compound derived
from reverse esters thereof, m is an integer between about 5 to
about 22; and x is an integer between about 0 to about 1000;
wherein said composition has at least 1 compound derived from said
partially esterified ester-containing group or said reverse ester
thereof.
15. The process according to claim 14, further comprising a
silicone-containing surfactant.
16. The process according to claim 14, further comprising mixing at
least one additional additive selected from the group consisting
of: emollients, humectants, antiseptics, antioxidants, chelating
agents, ultraviolet absorbers, colorants, fragrances and
preservatives.
17. The process according to claim 14, wherein said composition is
a deodorant, antiperspirant, sunscreen, insect repellent or
anti-fungal agent.
18. A cosmetic composition comprising: (a) an aqueous phase
comprising: (i) water, and (ii) at least one cosmetically active
ingredient; (b) a coupling agent; and (c) an oil phase comprising:
(i) an isoparaffin solvent, and (ii) a silicone-containing solvent
having the formula: ##STR00078## wherein R.sup.4 is selected from
the group consisting of: alkyl and a group represented by the
formula: ##STR00079## wherein: a is an integer in the range between
about 1 to about 20; b is an integer in the range between about 0
to about 1000; R.sup.3 is a compound derived from a partially
esterified ester residue; and m is an integer in the range between
about 5 to about 22; with the proviso that the R.sup.4 groups are
not all alkyls.
19. A composition for topical application to human skin, comprising
a biologically active material and a cosmetically suitable carrier,
wherein the cosmetically suitable carrier comprises: (a) an aqueous
phase comprising: (i) water, and (ii) at least one cosmetically
active ingredient; (b) a coupling agent; and (c) an oil phase
comprising: (i) an isoparaffin solvent, and (ii) a
silicone-containing solvent having the formula: ##STR00080##
wherein: R.sup.1 are independently selected from the group
consisting of: an alkyl having 1-5 carbon atoms, a substituted
alkyl having 1-5 carbon atoms optionally substituted by one or more
fluorine atoms, and a phenyl, and R.sup.2 is selected from the
group consisting of: hydrogen, alkyl of 1 to 45 carbon atoms,
substituted alkyl of 1 to 45 carbon atoms optionally substituted by
one or more fluorine atoms, aryl, a partially esterified
ester-containing group represented by the formula: ##STR00081## and
a reverse ester thereof represented by the formula: ##STR00082##
and the formula: ##STR00083## and a reverse ester thereof
represented by the formula: ##STR00084## provided that if R.sup.1
is anything but methyl or ethyl, then R.sup.2 must be a methyl,
ethyl or butyl, R.sup.3 is derived from a partially esterified
ester residue; R.sup.8 is selected from the group consisting of:
hydrogen, alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to
45 carbon atoms optionally substituted by one or more fluorine
atoms, aryl and a compound derived from a partially esterified
ester residue; R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene; R.sup.4 is selected from the group
consisting of: alkyl of 1 to 45 carbon atoms, substituted alkyl of
1 to 45 carbon atoms optionally substituted by one or more fluorine
atoms, aryl, said ester-containing group and said compound derived
from reverse esters thereof, m is an integer between about 5 to
about 22; and x is an integer between about 0 to about 1000;
wherein said composition has at least 1 compound derived from said
partially esterified ester-containing group or said reverse ester
thereof.
20. The composition according to claim 19, wherein said
cosmetically suitable carrier exhibits at least one property
selected from the group consisting of: substantially odor-free; a
refractive index in the range between about 1.41_to about 1.46;
solubility parameters in the range between about .sub.--7_to about
.sub.--9.+-.1.5_'d(i)@25.degree. C. (cal/cc) 1/2; viscosity in the
range between about 35_to about 2450_cSt@25.degree. C.; and surface
tension in the range between about 20 to about 23_dynes/cm.
21. The composition according to claim 19, wherein said composition
is one selected from the group consisting of: sunscreens, shampoos,
lip balms, moisturizing lotions, and antiperspirants.
22. A method of making a composition for topical application to
human skin, comprising a biologically active material and a
cosmetically suitable carrier, comprising combining a mixed feed
silicone ester into a carrier to produce a cosmetically suitable
carrier, wherein the cosmetically suitable carrier comprises 5-05
wt % of the mixed feed silicone ester based on the total weight of
the composition, wherein the mixed feed silicone ester comprises: a
silicone-containing solvent having the formula: ##STR00085##
wherein: R.sup.1 are independently selected from the group
consisting of: an alkyl having 1-5 carbon atoms, a substituted
alkyl having 1-5 carbon atoms optionally substituted by one or more
fluorine atoms, and a phenyl, and R.sup.2 is selected from the
group consisting of: hydrogen, alkyl of 1 to 45 carbon atoms,
substituted alkyl of 1 to 45 carbon atoms optionally substituted by
one or more fluorine atoms, aryl, a partially esterified
ester-containing group represented by the formula: ##STR00086## and
a reverse ester thereof represented by the formula: ##STR00087##
and the formula: ##STR00088## and a reverse ester thereof
represented by the formula: ##STR00089## provided that if R.sup.1
is anything but methyl or ethyl, then R.sup.2 must be a methyl,
ethyl or butyl, R.sup.3 is derived from a partially esterified
ester residue; R.sup.8 is selected from the group consisting of:
hydrogen, alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to
45 carbon atoms optionally substituted by one or more fluorine
atoms, aryl and a compound derived from a partially esterified
ester residue; R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene; R.sup.4 is selected from the group
consisting of: alkyl of 1 to 45 carbon atoms, substituted alkyl of
1 to 45 carbon atoms optionally substituted by one or more fluorine
atoms, aryl, said ester-containing group and said compound derived
from reverse esters thereof, m is an integer between about 5 to
about 22; and x is an integer between about 0 to about 1000;
wherein said composition has at least 1 compound derived from said
partially esterified ester-containing group or said reverse ester
thereof.
Description
FIELD OF THE INVENTION
[0001] The present disclosure relates to dispersion of inorganic
compounds, such as zinc oxide compounds, using silicone based
fluids having silicon groups and organic groups linked through
ester linkages. The silicone based fluids are preferably formed
from the reaction of vinyl-terminated carboxylic acid esters of
partially esterified esters with hydride containing polysiloxanes.
The vinyl-terminated carboxylic acid esters of partially esterified
esters are formed from the reaction of multifunctional alcohols
with vinyl-terminated carboxylic acids. Preferably, the resultant
formulation is useful in sunscreen, antiperspirant/deodorant and
facial makeup formulations at lower concentrations because of their
superior dispersing properties.
BACKGROUND OF THE INVENTION
[0002] Antiperspirant and deodorant products are well-known in the
cosmetic art. They are generally used by rubbing an area of the
body such as the underarm to apply a layer of the composition to
the skin which reduces odor and/or perspiration. It is desirable
that such products have aesthetic characteristics of non-crumbling,
smoothness, non-oiliness and non-tackiness. Clarity of such
products is a long-sought desirable aesthetic characteristic.
Another desirable characteristic is that no readily visible residue
as, e.g., a white layer, be left on the skin after the deodorant or
antiperspirant is applied.
[0003] Antiperspirant and deodorant products have appeared in the
marketplace in various dosage forms, such as sticks, gels,
roll-ons, aerosols and creams. Generally, these dosage forms
include a solution of the active ingredient in a suitable solvent,
a suspension of the active ingredient in a non-solvent, or a
multiphase dispersion or emulsion in which a solution of the active
ingredient is dispersed in some continuous phase or in which the
solubilized active ingredient constitutes the continuous phase.
[0004] The stick form has become the dominant antiperspirant dosage
form in the United States market, constituting more than 50% of
total antiperspirant sales, and is popular to varying degrees
globally. Cosmetically acceptable antiperspirant sticks typically
consist of a suspension of spray-dried active antiperspirant
material in vehicles such as cyclomethicone, with a waxy substance
such as stearyl alcohol, alone or in combination with castor wax,
gelling or thickening the suspension sufficiently to create a
suitable stick.
[0005] The stick form can be distinguished from a gel or a paste in
that in a stick, the formulated product can maintain its shape for
extended time periods outside the package, the product not losing
its shape significantly (allowing for some shrinkage due to solvent
evaporation).
[0006] The hard stick dosage form, although widely accepted by the
consumer, suffers from leaving a white residue on skin after
application, and can cause staining of fabric, which is considered
to be undesirable, particularly by female consumers. The gel dosage
form can be formulated to reduce and/or eliminate the white
residue.
[0007] One such clear gel antiperspirant is set forth in
International Patent Application No. WO 92/05767, published on Apr.
16, 1992 (The Gillette Company), which is incorporated herein by
reference. This patent application pertains generally to a clear
gel-type cosmetic product which includes an emulsion with an oil
phase and a water phase that includes an incorporated active
ingredient. The oil phase preferably makes up about 10 to 25% of
the product and includes an emulsifier which when properly mixed
with the water phase components yields a water-in-oil emulsion. The
oil phase is typically a blend of liquids and includes a
polyorganosiloxane (e.g., dimethicone) and a silicone emulsifying
agent. A particularly suitable emulsifying agent is a polyether
substituted silicone of cyclomethicone and dimethicone copolyol.
This emulsifier is useful for preparing stable water-in-oil
silicone emulsions where silicone makes up a large portion of the
oil phase, and is a dispersion of a silicone surfactant (i.e.,
dimethicone copolyol), i.e., 10% silicone surfactant in
cyclomethicone (i.e., a silicone solvent). The water phase includes
one or more polar species such as water, propylene glycol, sorbitol
and ethanol. The water phase includes, in solution, a deodorant
and/or antiperspirant active ingredient such a triclosan,
benzethonium chloride and/or an astringent salt of aluminum or
zirconium, such as aluminum chlorohydrate or aluminum zirconium
tetrachlorohydrex-glycine. The gel can also contain additional
cosmetic ingredients such as emollients, colorants, fragrances, and
preservatives.
[0008] It has been unexpectedly discovered that ester
functionalized silicones of the present disclosure raises and
improves the refractive index (RI) of the silicone significantly,
which provides great benefit in personal care applications. That
is, such formulations will show benefit as antiwhitening agents in
antiperspirants and sunscreens.
[0009] These unique ester functionalized silicones maintain the
same great surface tension property of silicone, i.e., provide the
same spreading and silky feel as silicone in personal care
formulations.
[0010] In addition to the two properties mentioned above, the
silicone esters of the present disclosure provide enhanced
formulation flexibility and provide ease to integrate various
components that are not mixable otherwise.
[0011] Some examples of conventional gel antiperspirants and
deodorants are set forth below:
[0012] Antiperspirant Water Phase Water 37.01% Aluminum
Chlorohydrate 30.00% Ethanol 10.00% Propylene Glycol 4.99% Oil
Phase Dimethicone 9.85% Cyclomethicone & Dimethicone Copolyol
8.00% Fragrance 0.15% Deodorant Water Phase Water 33.25% Sorbitol
14.00% Ethanol 12.00% Propylene Glycol 22.50% Triclosan 0.25%
Sodium Hydroxide 0.02% Oil Phase Dimethicone 9.70% Cyclomethicone
& Dimethicone Copolyol 8.00% Fragrance 0.30%.
[0013] International Patent Application No. WO 97/06777, which is
incorporated herein by reference, also discloses a clear cosmetic
gel composition which includes: (1) an aqueous phase containing
water and at least one cosmetically active ingredient, (2) an oil
phase containing a high refractive index material, (3) at least one
coupling agent to bring the aqueous phase and the oil phase into a
homogeneous composition, and (4) an alkoxylated, alkyl substituted
siloxane surface active agent in an amount sufficient to form the
composition into a water-in-oil emulsion. The oil phase includes a
volatile silicone fluid, a non-volatile silicone fluid and an
emollient. The emollient is preferably phenyl trimethicone.
[0014] U.S. Pat. No. 4,900,542 (Parrotta, Jr., et al.), which
issued on Feb. 13, 1990 and which is incorporated herein by
reference, discloses a process for preparing uniform, clear,
microcrystalline emulsion antiperspirant compositions of gel-like
consistency comprising: mixing the antiperspirant active material
with water, charging the aqueous phase into an oil-alcohol phase
containing a volatile silicone, a silicone emulsifier, a
non-volatile emollient and a coupling agent, heating the resultant
mixture with agitation until a uniform mixture is obtained,
homogenizing the mixture and passing the homogenized mixture to a
holding tank or directly to a filter.
[0015] The clear gel antiperspirants and deodorants described above
are based on water-in-oil emulsions which are stabilized with a
silicone surfactant. The silicone surfactant is commercially
available as a 10 wt. % solution in a volatile silicone solvent,
such as cyclomethicone (also known as decamethycyclopentasiloxane
and/or octamethylcyclotetrasiloxane).
[0016] Esters have been used for a number of years for a variety of
personal care applications including solids dispersion. The esters
are fully esterified, i.e., for esters of polyhydric alcohols,
nearly all the hydroxyl groups have been reacted with acids so that
the hydroxyl number is generally less than about 5.
[0017] Zinc oxides have been used in the cosmetics industry as a
potent sunscreen in concentrations in the range between 2 to 10%
usually in oil-in-water formulations. To be effective it must be
well dispersed to coat the skin evenly to prevent harmful
ultraviolet (UV) rays from reaching the skin surface. If not
dispersed effectively agglomeration occurs resulting in uneven
distribution over the skin surface resulting in UV penetration of
gaps in the surface layering.
[0018] The present inventors have discovered that utilization of a
silicone based fluid made with partially esterified esters as a
dispersing agent provides desired branching and reactive
intermediates to effectively disperse inorganic solids, such as
zinc oxide, thereby reducing the amount of zinc oxide required for
use in personal care applications, such as sunscreens and color
cosmetics.
SUMMARY OF THE INVENTION
[0019] A cosmetic composition comprising: (a) an aqueous phase
comprising: (i) water, and (ii) at least one cosmetically active
ingredient; (b) a coupling agent; and (c) an oil phase comprising:
(i) an isoparaffin solvent, and (ii) a silicone-containing solvent
having the formula:
##STR00002##
wherein:
[0020] R.sup.1 are independently selected from the group consisting
of: an alkyl having 1-5 carbon atoms, a substituted alkyl having
1-5 carbon atoms optionally substituted by one or more fluorine
atoms, and a phenyl, and R.sup.2 is selected from the group
consisting of: hydrogen, alkyl of 1 to 45 carbon atoms, substituted
alkyl of 1 to 45 carbon atoms optionally substituted by one or more
fluorine atoms, aryl, a partially esterified ester-containing group
represented by the formula:
##STR00003##
and a reverse ester thereof represented by the formula:
##STR00004##
and the formula:
##STR00005##
and a reverse ester thereof represented by the formula:
##STR00006##
provided that if R.sup.1 is anything but methyl or ethyl, then
R.sup.2 must be a methyl, ethyl or butyl,
[0021] R.sup.3 is derived from a partially esterified ester
residue;
[0022] R.sup.8 is selected from the group consisting of: hydrogen,
alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon
atoms optionally substituted by one or more fluorine atoms, aryl
and a compound derived from a partially esterified ester
residue;
[0023] R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene;
[0024] R.sup.4 is selected from the group consisting of: alkyl of 1
to 45 carbon atoms, substituted alkyl of 1 to 45 carbon atoms
optionally substituted by one or more fluorine atoms, aryl, the
ester-containing group and the compound derived from reverse esters
thereof,
[0025] m is an integer between about 5 to about 22; and
[0026] x is an integer between about 0 to about 1000;
wherein the composition has at least 1 compound derived from the
partially esterified ester-containing group or the reverse ester
thereof.
[0027] Preferably, the isoparaffin solvent has a boiling range
between about 100 to 340.degree. C., wherein the isoparaffin
constitutes between about 1 to 75% by weight, of the total of the
oil phase.
[0028] The composition further comprising (d) a silicone-containing
surfactant. The silicone-containing surfactant is an alkoxylated,
alkyl substituted siloxane surface active agent. The
silicone-containing surfactant is dimethicone copolyol or a mixture
of dimethicone copolyol and cyclomethicone. The silicone-containing
surfactant is present in an amount between about 0.2 to 2% by
weight, of the total weight of the composition.
[0029] The coupling agent is present in an amount between about 10
to 30% by weight, of the total weight of the composition.
[0030] The isoparaffin solvent is a saturated aliphatic hydrocarbon
containing at least one side chain, and wherein the total carbon
atoms are in the range between about 8 to 20. The isoparaffin
constitutes between about 25 to 50% by weight, of the total of the
oil phase.
[0031] The composition further comprises at least one additional
additive selected from the group consisting of: emollients,
humectants, antiseptics, antioxidants, chelating agents,
ultraviolet absorbers, colorants, fragrances and preservatives.
[0032] The composition is a deodorant, antiperspirant, sunscreen,
insect repellent or anti-fungal agent.
[0033] A process for preparing a clear cosmetic composition
comprising mixing the following: an aqueous phase comprising: (i)
water, and (ii) at least one cosmetically active ingredient; a
coupling agent; an oil phase comprising: (i) an isoparaffin
solvent, and (ii) a silicone-containing solvent having the
formula:
##STR00007##
wherein:
[0034] R.sup.1 are independently selected from the group consisting
of: an alkyl having 1-5 carbon atoms, a substituted alkyl having
1-5 carbon atoms optionally substituted by one or more fluorine
atoms, and a phenyl, and R.sup.2 is selected from the group
consisting of: hydrogen, alkyl of 1 to 45 carbon atoms, substituted
alkyl of 1 to 45 carbon atoms optionally substituted by one or more
fluorine atoms, aryl, a partially esterified ester-containing group
represented by the formula:
##STR00008##
and a reverse ester thereof represented by the formula:
##STR00009##
and the formula:
##STR00010##
and a reverse ester thereof represented by the formula:
##STR00011##
provided that if R.sup.1 is anything but methyl or ethyl, then
R.sup.2 must be a methyl, ethyl or butyl,
[0035] R.sup.3 is derived from a partially esterified ester
residue;
[0036] R.sup.8 is selected from the group consisting of: hydrogen,
alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon
atoms optionally substituted by one or more fluorine atoms, aryl
and a compound derived from a partially esterified ester
residue;
[0037] R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene;
[0038] R.sup.4 is selected from the group consisting of: alkyl of 1
to 45 carbon atoms, substituted alkyl of 1 to 45 carbon atoms
optionally substituted by one or more fluorine atoms, aryl, the
ester-containing group and the compound derived from reverse esters
thereof,
[0039] m is an integer between about 5 to about 22; and
[0040] x is an integer between about 0 to about 1000;
wherein the composition has at least 1 compound derived from the
partially esterified ester-containing group or the reverse ester
thereof.
[0041] Additionally, the cosmetic composition may also comprise:
(a) an aqueous phase comprising: (i) water, and (ii) at least one
cosmetically active ingredient; (b) a coupling agent; and (c) an
oil phase comprising: (i) an isoparaffin solvent, and (ii) a
silicone-containing solvent having the formula:
##STR00012##
[0042] wherein R.sup.4 is selected from the group consisting of:
alkyl and a group represented by the formula:
##STR00013##
wherein:
[0043] a is an integer in the range between about 1 to about
20;
[0044] b is an integer in the range between about 0 to about
1000;
[0045] R.sup.3 is a compound derived from a partially esterified
ester residue; and
[0046] m is an integer in the range between about 5 to about
22;
with the proviso that the R.sup.4 groups are not all alkyls.
[0047] A composition for topical application to human skin,
comprising a biologically active material and a cosmetically
suitable carrier, wherein the cosmetically suitable carrier
comprises: (a) an aqueous phase comprising: (i) water, and (ii) at
least one cosmetically active ingredient; (b) a coupling agent; and
(c) an oil phase comprising: (i) an isoparaffin solvent, and (ii) a
silicone-containing solvent having the formula:
##STR00014##
wherein:
[0048] R.sup.1 are independently selected from the group consisting
of: an alkyl having 1-5 carbon atoms, a substituted alkyl having
1-5 carbon atoms optionally substituted by one or more fluorine
atoms, and a phenyl, and R.sup.2 is selected from the group
consisting of: hydrogen, alkyl of 1 to 45 carbon atoms, substituted
alkyl of 1 to 45 carbon atoms optionally substituted by one or more
fluorine atoms, aryl, a partially esterified ester-containing group
represented by the formula:
##STR00015##
and a reverse ester thereof represented by the formula:
##STR00016##
and the formula:
##STR00017##
and a reverse ester thereof represented by the formula:
##STR00018##
provided that if R.sup.1 is anything but methyl or ethyl, then
R.sup.2 must be a methyl, ethyl or butyl,
[0049] R.sup.3 is derived from a partially esterified ester
residue;
[0050] R.sup.8 is selected from the group consisting of: hydrogen,
alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon
atoms optionally substituted by one or more fluorine atoms, aryl
and a compound derived from a partially esterified ester
residue;
[0051] R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene;
[0052] R.sup.4 is selected from the group consisting of: alkyl of 1
to 45 carbon atoms, substituted alkyl of 1 to 45 carbon atoms
optionally substituted by one or more fluorine atoms, aryl, the
ester-containing group and the compound derived from reverse esters
thereof,
[0053] m is an integer between about 5 to about 22; and
[0054] x is an integer between about 0 to about 1000;
wherein the composition has at least 1 compound derived from the
partially esterified ester-containing group or the reverse ester
thereof.
[0055] Wherein the cosmetically suitable carrier exhibits at least
one property selected from the group consisting of: [0056]
substantially odor-free; [0057] a refractive index in the range
between about 1.41_to about 1.46; [0058] solubility parameters in
the range between about .sub.--7_to
about.sub.--9.+-.1.5_'d(i)@25.degree. C. (cal/cc) 1/2_; [0059]
viscosity in the range between about 35_to about
.sub.--2450_cSt@25.degree. C_; [0060] surface tension in the range
between about 20 to about 23_dynes/cm_; and [0061] mixtures
thereof.
[0062] The composition is one selected from the group consisting
of: sunscreens, shampoos, lip balms, moisturizing lotions, and
antiperspirants.
[0063] A method of making a composition for topical application to
human skin, comprising a biologically active material and a
cosmetically suitable carrier, comprising combining a mixed feed
silicone ester into a carrier to produce a cosmetically suitable
carrier, wherein the cosmetically suitable carrier comprises 5-05
wt % of the mixed feed silicone ester based on the total weight of
the composition, wherein the mixed feed silicone ester comprises: a
silicone-containing solvent having the formula:
##STR00019##
wherein:
[0064] R.sup.1 are independently selected from the group consisting
of: an alkyl having 1-5 carbon atoms, a substituted alkyl having
1-5 carbon atoms optionally substituted by one or more fluorine
atoms, and a phenyl, and R.sup.2 is selected from the group
consisting of: hydrogen, alkyl of 1 to 45 carbon atoms, substituted
alkyl of 1 to 45 carbon atoms optionally substituted by one or more
fluorine atoms, aryl, a partially esterified ester-containing group
represented by the formula:
##STR00020##
and a reverse ester thereof represented by the formula:
##STR00021##
and the formula:
##STR00022##
and a reverse ester thereof represented by the formula:
##STR00023##
provided that if R.sup.1 is anything but methyl or ethyl, then
R.sup.2 must be a methyl, ethyl or butyl,
[0065] R.sup.3 is derived from a partially esterified ester
residue;
[0066] R.sup.8 is selected from the group consisting of: hydrogen,
alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon
atoms optionally substituted by one or more fluorine atoms, aryl
and a compound derived from a partially esterified ester
residue;
[0067] R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene;
[0068] R.sup.4 is selected from the group consisting of: alkyl of 1
to 45 carbon atoms, substituted alkyl of 1 to 45 carbon atoms
optionally substituted by one or more fluorine atoms, aryl, the
ester-containing group and the compound derived from reverse esters
thereof,
[0069] m is an integer between about 5 to about 22; and
[0070] x is an integer between about 0 to about 1000;
wherein the composition has at least 1 compound derived from the
partially esterified ester-containing group or the reverse ester
thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0071] FIG. 1 is a graph depicting an arbitrary rating system that
has been established to compare the efficacy of certain
conventional dispersion compositions versus the compositions of the
present disclosure.
[0072] FIG. 2 is a table which provides comparative data relating
to Brookfield viscosity when Z-Cote HP-1 (a zinc oxide product
coated with triethyoxy caprylyl silane) is dispersed in
conventional full ester products, such as PureSyn6, PureSyn 3E20
and MCP 2262, versus dispersion characteristics when dispersed in
fluids formed from silicon-based partial esters according to the
present disclosure.
[0073] FIG. 3 is a graph Brookfield viscosity versus solids loading
amounts for the conventional full ester dispersions and fluid
formed from silicon-based partial esters according to the present
disclosure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0074] A clear cosmetic composition comprising: (a) an aqueous
phase comprising: (i) water, and (ii) at least one cosmetically
active ingredient; (b) a coupling agent; (c) an oil phase
comprising: (i) a silicone-containing solvent, and (ii) an
isoparaffin solvent having a boiling range between about 100 to
340.degree. C., wherein the isoparaffin constitutes between about 1
to 75% by weight, of the total of the oil phase; and (d)
silicone-containing surfactant.
[0075] The silicone-containing surfactant is preferably an
alkoxylated, alkyl substituted siloxane surface active agent, e.g.,
dimethicone copolyol or a mixture of dimethicone copolyol and
cyclomethicone. This silicone-containing surfactant is present in
an amount between about 0.2 to 2% by weight, of the total weight of
the composition. The coupling agent is present in an amount between
about 10 to 30% by weight, of the total weight of the
composition.
[0076] The aqueous phase comprises water in an amount between about
20 to 70% by weight, of the total weight of the composition. The
oil phase comprises a silicone-containing solvent which includes a
volatile silicone fluid and a non-volatile silicone fluid. The
volatile silicone fluid is preferably a cyclomethicone and the
non-volatile silicone fluid is preferably dimethicone. The
preferred mixture of the oil phase and the silicone-containing
surfactant comprises between about 10 to 30% by weight, of the
total weight of the composition, and the mixture of the aqueous
phase and the coupling agent comprises between about 70 to 90% by
weight, of the total weight of the composition.
[0077] Optionally, the isoparaffin can replace at least a portion
of the dimethicone such that the oil phase has essentially the same
viscosity as the original oil phase. The molecular weight of the
dimethicone may need to be simultaneously increased to achieve this
viscosity.
[0078] By isoparaffin is meant a saturated aliphatic hydrocarbon
whose molecules have at least one carbon atom bonded to at least
three other carbon atoms or at least one side chain (i.e., a
molecule having one or more tertiary or quaternary carbon atoms),
and preferably wherein the total number of carbon atoms per
molecule is in the range between about 8 to 20, more preferably 10
to 20. Various isomers of each carbon number will typically be
present in the solvent. The isoparaffins may also include
cycloparaffins with branched side chains, generally as a minor
component of the isoparaffin solvent. The isoparaffin solvent may
contain molecules have a carbon number (e.g., a narrow cut such as
isomers having a range between about C.sub.10 to C.sub.12, or a
wide cut such as isomers having between about C.sub.11 to
C.sub.18). The vapor pressure of the isoparaffin is also preferably
not greater than 2 mm Hg at 20.degree. C. for antiperspirant and
deodorant products. Preferably, the isoparaffin constitutes between
about 25 to 50% by weight, of the total of the oil phase.
[0079] The clear cosmetic composition of the present disclosure may
further comprise at least one additional additive selected from the
group consisting of: emollients, humectants, antiseptics,
antioxidants, chelating agents, ultraviolet absorbers, colorants,
fragrances and preservatives. This composition is preferably either
a deodorant, antiperspirant, sunscreen, insect repellent or
anti-fungal agent.
[0080] The present disclosure also pertains to a process for
preparing a clear cosmetic composition comprising mixing the
following: an aqueous phase comprising: (i) water, and (ii) at
least one cosmetically active ingredient; a coupling agent; an oil
phase comprising: (i) a silicone-containing solvent, and (ii) an
isoparaffin solvent having a boiling range between about 100 to
340.degree. C., wherein the isoparaffin constitutes between about 1
to 75% by weight, of the total of the oil phase; and
silicone-containing surfactant.
[0081] Another embodiment of the present disclosure includes a
clear cosmetic composition comprising: (a) an aqueous phase
comprising: (i) water, and (ii) at least one cosmetically active
ingredient; (b) a coupling agent; (c) an oil phase comprising: a
silicone-containing solvent comprising a volatile silicone fluid
and a non-volatile silicone fluid, and wherein at least a portion
of the non-volatile silicone fluid is replaced with an isoparaffin
solvent having a boiling range between about 200 to 340.degree. C.,
wherein the viscosity of the non-volatile silicone/isoparaffin
solution is in the range between about 10 to 100 cps at a
temperature between about 20 to 25.degree. C.; and (d)
silicone-containing surfactant. Preferably, the volatile silicone
fluid is cyclomethicone and the non-volatile silicone fluid is
dimethicone. Optionally, the isoparaffin has a flash point in the
range between about 60 to 150.degree. C. and the non-volatile
silicone fluid has a viscosity of no greater than 10,000 cSt.
[0082] Throughout the present disclosure, the present disclosure is
described primarily in connection with a clear soft gel
antiperspirant composition. However, the present disclosure is not
limited to soft gel compositions or to antiperspirant compositions.
For example, compositions according to the present disclosure can
be clear deodorant compositions. Moreover, depending on additional
or other active ingredients included in the composition, the
composition can also be an emollient composition, an analgesic
(methyl salicylate) composition, a sunscreen composition, etc.
Various active materials incorporated in cosmetic compositions are
disclosed in U.S. Pat. No. 4,322,400 to Yuhas, the contents of
which are incorporated herein by reference in their entirety.
[0083] Throughout the present specification, "active
antiperspirant" and "active deodorant" materials are discussed.
Both types of materials contribute to reduction of body malodor. By
reduction of body malodor, we mean that, generally, there is less
body malodor after application of a composition to the person's
skin as compared to the person's body malodor without application
of the composition. Such reduction can be due to a masking of the
malodor, absorption and/or chemical reaction of the malodorous
material, reduction of levels of the bacteria producing the
malodorous material, e.g., from perspiration, reduction of
perspiration, etc. The antiperspirant active materials, when
utilized in an antiperspirant effective amount in the composition,
act to reduce body malodor by reducing production of perspiration;
however, these antiperspirant active materials can also have a
deodorant function, e.g., as an antimicrobial agent. The deodorant
active materials do not substantially reduce the production of
perspiration, but reduce malodor in other ways, e.g., as fragrances
masking the malodor or reducing the malodor intensity, as odor
absorbents, as antimicrobial agents, as agents chemically reacted
with malodorous materials, etc.
[0084] A desired feature of the present disclosure is that a clear,
or transparent, cosmetic composition (e.g., clear or transparent
deodorant or antiperspirant gel composition) can be provided. The
term clear or transparent (that is clarity), according to the
present disclosure, is intended to connote its usual dictionary
definition; thus, a clear, e.g., cosmetic composition at the
present disclosure allows ready viewing of objects behind it. By
contrast, a translucent composition allows light to pass through,
but causes the light to be so scattered that it will be impossible
to see clearly objects behind the translucent composition.
[0085] The present disclosure contemplates a clear cosmetic
composition which is a water-in-oil emulsion. The aqueous phase of
this emulsion contains water and at least one cosmetically active
ingredient, with the cosmetically active ingredient being in the
composition in an amount so as to have a cosmetic effect. The oil
phase of the emulsion includes a high refractive index material (a
material having a refractive index in the range of 1.40-1.50) and
desirably also includes silicone surfactants, and preferably
contains both volatile and non-volatile silicone solvents.
Optionally, the compositions according to the present disclosure
also include at least one coupling agent to bring the aqueous phase
and the oil phase into a homogeneous composition. Moreover, the
clear cosmetic composition of the present disclosure, which is in
the form of a macro-emulsion as contrasted to a micro-emulsion,
does not need to contain wax or gelling agents such as soaps,
cellulosic materials or algenites.
[0086] The gel emulsions according to the present disclosure are
stable and optically clear, are cosmetically elegant, and are
capable of being delivered from a suitable applicator package. They
are easily applied to the skin and have a smooth, silky feel and a
cool sensation, yet are fast-drying and non-tacky. These
compositions of the present disclosure may be prepared by a batch
process, or a continuous or semi-continuous process, and the
processes yield compositions which are stable, highly efficacious
and possess excellent aesthetic qualities.
[0087] Where the composition is an antiperspirant gel composition,
any of the known antiperspirant active materials can be utilized in
the composition at the present disclosure. Suitable materials which
may be mentioned by way of example include aluminum chlorohydrate,
aluminum chloride, aluminum sesquichlorohydrate, aluminum-zirconium
hydroxychlorides, complexes or adducts of the above-mentioned
active ingredients with glycol, such as propylene glycol, and
combinations thereof. Known aluminum-zirconium salts in combination
with neutral amino acids, such as glycine (e.g., aluminum-zirconium
tetrachlorohydroxy) can also be used. Generally, any of the
Category I active antiperspirant ingredients, listed in the Food
and Drug Administration's Monograph on Antiperspirant Drug Products
for overall-the-counter human use (Oct. 10, 1973) can be used. In
addition, any new ingredient, not listed in the Monograph, such as
aluminum nitrohydrate and its combination with zirconyl
hydroxychlorides and nitrates, or aluminum-stannous chlorohydrates,
can be incorporated as an antiperspirant active ingredient in
antiperspirant compositions according to the present
disclosure.
[0088] The preferred antiperspirant materials include aluminum
zirconium tetrachlorohydrate and aluminum chlorohydrate.
[0089] The amount of active component that can be used will vary
with the particular active ingredient incorporated. As a general
rule, an antiperspirant product should contain an active
antiperspirant material in an amount anywhere from about 10% to
about 35% by weight, of the total weight of the composition, more
preferably from about 20% to about 30% by weight, of the total
weight of the composition. The active antiperspirant material
utilized in the compositions of the present disclosure can be
pre-dissolved in water or in another solvent (for example, in
propylene glycol) or can be in powdered form, and may be buffered
or unbuffered. Preferably, the antiperspirant materials are present
in solution in a solvent therefor.
[0090] Where a deodorant active material is utilized, any deodorant
active material which can be dissolved in the aqueous phase can be
utilized. Illustratively, the deodorant active material can be
2,4,4'-trichloro-2'-hydroxy diphenyl ether (triclosan), and/or
benzethonium chloride. Where the deodorant ingredient is used in
place of the antiperspirant active ingredient, a deodorant gel
composition (rather than an antiperspirant gel composition) would
be provided.
[0091] Amounts of cosmetically active ingredients incorporated are
those sufficient to have a cosmetic effect. For example, where a
deodorant active ingredient such as triclosan is incorporated,
amounts thereof as conventionally used in the art can be
incorporated in the composition according to the present
disclosure.
[0092] The aqueous phase includes one or a combination of various
polar species, and includes at least water (refractive index of
1.3333). Other polar species include polyhydric alcohols and
derivatives thereof (e.g., esters and ethers thereof).
Illustratively, water can be included in the composition in an
amount in the range of 20% to 70% by weight, of the total weight of
the composition.
[0093] At least one coupling agent is included in the composition
of the present disclosure. Such coupling agent is illustratively
(but not limited to) the following: [0094] Coupling Agents Ethyl
alcohol Ethylene glycol monoethyl ether 2-ethylhexanol Diethylene
glycol monoethyl ether Ethylene carbonate Propoxylated oleyl
alcohol N-methylglucamine Butyl stearate Linear ethoxylated polymer
of Butyl myristate methanol Isopropyl alcohol SD-40 alcohol
PPG-(2-5) lanolate PPG (2-8) myristyl ether PPG-(2-8) isostearate
PPG (2-8) lauryl ether Propylene glycol (2) methyl ether
Dipropylene glycol PPG-(2-3) methyl ether PPG (2-10) cetyl ether
PPG-14 butyl ether PEG-6 diisopropyl adipate Ethoxylated (2-20
moles) glucose Methoxy PEG-22 dodecyl-glycol Propoxylated (2-20
moles) glucose copolymer PPG-15 Stearyl ether PEG-30 Glyceryl
monoacetate PPG-(5-20) methyl glucose ether Sorbitol Isoprene
glycol PEG-3 oleyl ether phosphate Propylene carbonate PEG-(2-5)
oleyl ether Glycerine
[0095] This coupling agent acts to stabilize the emulsion and also
acts as a clarifying agent. Moreover, various of these coupling
agents, such as SD-40 alcohol, aid in drying and has a cooling
effect, providing advantageous aesthetic properties for the
composition.
[0096] The coupling agent is preferably a low molecular weight
alcohol such as, but not limited to, an alcohol having from about 2
to about 10 carbon atoms, preferably from about 2 to about 4 carbon
atoms; or a glycol such as, but not limited to, propylene glycol,
ethylene glycol, isoprene glycol and dipropylene glycol; glycerine,
sorbitol and/or propylene carbonate. The coupling agent can be one
compound or a mixture of compounds.
[0097] Illustratively, the coupling agent is present in an amount
of from about 10% to about 30% by weight, preferably from about 14%
to about 25% by weight, of the total weight of the composition.
[0098] The oil phase according to the present disclosure is
desirably, a silicone oil/isoparaffin solution, so as to provide a
water-in-oil emulsion. The total of oil phase and siloxane surface
active agent preferably makes up from about 8% to about 30% by
weight, of the total weight of the composition. This surface active
agent is an emulsifier which, when properly mixed with the aqueous
phase components, oil phase components and coupling agents, yields
a water-in-oil emulsion. The oil phase is desirably a blend of
liquids.
[0099] The oil phase can include, illustratively, a
silicone-containing solvent having the general formula:
##STR00024##
wherein:
[0100] R.sup.1 are independently selected from the group consisting
of: an alkyl having 1-5 carbon atoms, a substituted alkyl having
1-5 carbon atoms optionally substituted by one or more fluorine
atoms, and a phenyl, and R.sup.2 is selected from the group
consisting of: hydrogen, alkyl of 1 to 45 carbon atoms, substituted
alkyl of 1 to 45 carbon atoms optionally substituted by one or more
fluorine atoms, aryl, an ester-containing group represented by the
formula:
##STR00025##
and a reverse ester thereof represented by the formula:
##STR00026##
and the formula:
##STR00027##
and a reverse ester thereof represented by the formula:
##STR00028##
provided that if R.sup.1 is anything but methyl or ethyl, then
R.sup.2 must be a methyl, ethyl or butyl,
[0101] R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00029##
wherein this case the two esterified groups on the molecule have
been reacted with heptanoic acid.
[0102] R.sup.8 is selected from the group consisting of: hydrogen,
alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon
atoms optionally substituted by one or more fluorine atoms, aryl
and a compound derived from a partially esterified ester
residue;
[0103] R.sup.9 is selected from the group consisting of: an
arylene, an alkylene of 1 to 22 carbon atoms, substituted alkylene
of 1 to 22 carbon atoms optionally substituted by one or more
fluorine atoms and arylene;
[0104] R.sup.4 is selected from the group consisting of: alkyl of 1
to 45 carbon atoms, substituted alkyl of 1 to 45 carbon atoms
optionally substituted by one or more fluorine atoms, aryl, said
ester-containing group and said compound derived from reverse
esters thereof,
[0105] m is an integer between about 5 to about 22; and
[0106] x is an integer between about 0 to about 1000;
[0107] wherein said composition has at least 1 compound derived
from said partially esterified ester-containing group or and said
reverse ester thereof.
[0108] Preferably, R.sup.1 and R.sup.2 are both methyl groups and m
is an integer between about 10 to about 14, preferably m is 10.
Moreover, x is an integer in the range between about 6 to about
110, preferably between about 6 to about 50.
[0109] The compound derived from said partially esterified ester
residue is a partially esterified alcohol. The
mono-hydroxy-terminated partially esterified alcohol is derived
from a poly-functional alcohol represented by the formula:
R.sup.5(OH).sub.n
wherein:
[0110] R.sup.5 is an n-functional hydrocarbon; and
[0111] n is from about 2 to about 8, preferably between about 2 to
about 4.
[0112] The functional alcohol is preferably selected from the group
consisting of: ethylene glycol, propylene glycol, butylene glycol,
polyethylene glycol, neopentyl glycol, polypropylene glycol,
glycerin, trimethylolethane, trimethylolpropane, pentaerythritol,
di-pentaerythritol, tri-pentaerythritol, and a mixture thereof. The
preferred functional alcohol is trimethylolpropane.
[0113] The compound derived from said partially esterified ester
residue is a partially esterified acid. The mono-hydroxy-terminated
partially esterified acid is derived from multi-functional acids.
The functional acid can be selected from the group consisting of
any C2 to C12 diacids, e.g., adipic, azelaic, sebacic, and
dodecanedioc, succinic acid, glutaric acid, maleic acid, phthalic
acid, trimellitic acid, nadic acid, methyl nadic acid,
hexahydrophthalic acid and mixtures thereof.
[0114] Anhydrides of polybasic acids can be used in place of the
multifunctional acids. The functional anhydride is selected from
the group consisting of: succinic anhydride, glutaric anhydride,
adipic anhydride, maleic anhydride, phthalic anhydride, trimellitic
anhydride, nadic anhydride, methyl nadic anhydride,
hexahydrophthalic anhydride, and mixtures thereof.
[0115] R.sup.4 is preferably a group represented by the
formula:
##STR00030##
wherein:
[0116] R.sup.3 is a compound derived from a partially esterified
ester residue;
[0117] m is an integer in the range between about 5 to about 22;
and
[0118] x is an integer in the range between about 0 to about
1000,
or a reverse ester thereof represented by the formula:
##STR00031##
wherein R.sup.8 is selected from the group consisting of: hydrogen,
alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon
atoms optionally substituted by one or more fluorine atoms, aryl
and a compound derived from a partially esterified ester
residue.
[0119] Alternatively, R.sup.4 is a methyl group.
[0120] The silicone-containing solvent may also be represented by
the formula:
##STR00032##
wherein:
[0121] R.sup.4 is selected from the group consisting of methyl and
a group represented by the formula:
##STR00033##
[0122] R.sup.3 is a compound derived from a partial ester
residue;
[0123] m is 10; and
[0124] x is an integer in the range between about 0 to about 1000,
preferably about 6 to about 110.
[0125] R.sup.4 is preferably a group represented by the
formula:
##STR00034##
wherein R.sup.3 is a compound derived from a partially esterified
ester residue. The partially esterified ester residue is derived
from a mono-hydroxy-terminated partially esterified alcohol. The
mono-hydroxy-terminated partially esterified alcohol is derived
from di-, tri- or tetra-functional alcohol represented by the
formula:
R.sup.5(OH).sub.n
wherein:
[0126] R.sup.5 is an n-functional hydrocarbon residue; and
[0127] n is an integer in the range between about 2 to about 8,
preferably between about 2 to about 4.
[0128] Preferably, the di-, tri- or tetra-functional alcohol is
selected from the group consisting of: ethylene glycol, propylene
glycol, butylene glycol, polyethylene glycol, neopentyl glycol,
polypropylene glycol, glycerin, trimethylolethane,
trimethylolpropane, pentaerythritol, di-pentaerythritol,
tri-pentaerythritol, and a mixture thereof.
[0129] Preferably, the functional alcohol is trimethylolpropane and
R.sup.4 is a group represented by the formula:
##STR00035##
wherein:
[0130] R.sup.3 is a compound derived from a partially esterified
ester residue;
[0131] m is an integer in the range between about 5 to about 22;
and
[0132] x is an integer in the range between about 0 to about
1000,
or a reverse ester thereof represented by the formula:
##STR00036##
wherein R.sup.8 is selected from the group consisting of: hydrogen,
alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to 45 carbon
atoms optionally substituted by one or more fluorine atoms, aryl
and a compound derived from a partially esterified ester residue.
Alternatively, R.sup.4 is a methyl group.
[0133] The partially esterified ester is represented by the
formula:
(R.sup.7COO).sub.n-1R.sup.6(OH)
wherein:
[0134] R.sup.6 is an (n-1)-functional hydrocarbon residue
group;
[0135] R.sup.7 is a hydrocarbyl group; and
[0136] n is an integer in the range between about 2 to about 8.
[0137] According to another embodiment of the present disclosure, a
silicone composition is represented by the formula:
##STR00037##
[0138] wherein R.sup.4 is selected from the group consisting of:
alkyl and a group represented by the formula:
##STR00038##
wherein:
[0139] a is an integer in the range between about 1 to about
20;
[0140] b is an integer in the range between about 0 to about
1000;
[0141] R.sup.3 is a compound derived from a partially esterified
ester residue; and
[0142] m is an integer in the range between about 5 to about
22;
with the proviso that the R.sup.4 groups are not all alkyls.
[0143] The alkoxylated, alkyl substituted siloxane surface active
agent is preferably, but not limited to, a dimethicone copolyol. An
illustrative alkoxylated silicone-containing surfactant utilizable
according to the present disclosure is cetyl dimethicone copolyol
referred to in U.S. Pat. No. 5,162,378 to Guthauser.
Illustratively, the alkoxylated, alkyl substituted siloxane surface
active agent is included in the composition in an amount of 0.2% to
2% by weight, of the total weight of the composition.
[0144] A specific cyclomethicone-dimethicone copolyol fluid which
can be utilized to provide the alkoxylated silicone containing
surface active agent is a mixture of cyclomethicone and dimethicone
copolyol designated as DC3225C from Dow Coming Corp or SF1328 from
General Electric Company. This is a polyether substituted silicone
of cyclomethicone and dimethicone copolyol (refractive index
(RI)=1.3994). This DC3225C, which is an emulsifying agent, is
useful for preparing stable water-in-oil emulsions where a silicone
makes up a large portion of the oil phase, and is a dispersion of a
silicone surfactant (dimethicone copolyol) (10% by wt.) in
cyclomethicone (Dow Corning 344 Fluid) (90% by wt.).
[0145] The mixture of cyclomethicone and dimethicone copolyol fluid
is present in the composition, illustratively, in an amount of from
about 4% to about 20% by weight, of the total weight of the
composition. The unique aspect according to the present disclosure
is that between 25-50% of the cyclomethicone in the dimethicone
copolyol dispersion is replaced with at least one isoparaffin
without any concomitant loss of properties, but with the added cost
benefits associated with the use of much cheaper isoparaffins.
[0146] Various materials which can be incorporated in the
water-based phase and in the oil-based phase are listed in
International Patent Application Publication No. WO 97/06777, which
is incorporated herein by reference, for example, emollients,
humectants, antiseptics, preservatives, antioxidants, chelating
agents, and U.V. absorbers.
[0147] While not limiting, in preferred embodiments the mixture of
oil phase and alkoxylated, alkyl substituted siloxane surface
active agent comprises from about 10% to about 30% by weight, of
the total weight of the composition, and the combination of aqueous
phase and coupling agents make up from about 70% to about 90% by
weight, of the total weight of the composition.
[0148] The metal oxide inorganic compound is at select one selected
from the group consisting of uncoated zinc oxide coated with
triethoxy caprylyl silane and titanium dioxide.
[0149] In addition the emollient formed by admixing the metal oxide
inorganic compound with the silicone compound formed partial esters
exhibit the following properties: a Brookfield viscosity at ambient
temperature in the range between about 100_to about 25000 cP at
ambient temperature.
[0150] In a preferred embodiment, R1 and R2 are independently
selected from hydrogen, alkyl of 1 to 45 carbon atoms, substituted
alkyl of 1 to 45 carbon atoms optionally substituted by one or more
fluorine atoms and aryl. More preferably, R1 and R2 are both methyl
groups.
[0151] Preferably, m is from about 10 to about 14, most preferably
m is 10.
[0152] Preferably, x is from about 6 to about 110, most preferably
x is from about 6 to about 50.
[0153] R3 is preferably a mono-hydroxy-terminated partially
esterified ester.
[0154] The mono-hydroxy-terminated partially esterified ester
residue is derived from a mono-hydroxy-terminated partially
esterified alcohol. That is, the mono-hydroxy-terminated partially
esterified alcohol is derived from di-, tri- or tetra-functional
alcohol represented by the formula:
R.sup.5(OH).sub.n
[0155] wherein:
[0156] R.sup.5 is an n-functional hydrocarbon residue; and
[0157] n is from about 2 to about 8, preferably from 2 to 4.
[0158] The functional alcohol is preferably selected from ethylene
glycol, propylene glycol, butylene glycol, polyethylene glycol,
neopentyl glycol polypropylene glycol, glycerin, trimethylolethane,
trimethylolpropane, pentaerythritol, di-pentaerythritol,
tri-pentaerythritol, and a mixture there, most preferably the
functional alcohol is trimethylolpropane.
[0159] R.sup.4 is a group represented by the formula:
##STR00039##
wherein:
[0160] R.sup.3 is a compound derived from a partially esterified
ester residue;
[0161] m is an integer in the range between about 5 to about 22;
and
[0162] x is an integer in the range between about 0 to about
1000,
or a reverse ester thereof represented by the formula:
##STR00040##
[0163] wherein R.sup.8 is selected from the group consisting of:
hydrogen, alkyl of 1 to 45 carbon atoms, substituted alkyl of 1 to
45 carbon atoms optionally substituted by one or more fluorine
atoms, aryl and a compound derived from a partially esterified
ester residue. Alternatively, R.sup.4 is a methyl group.
[0164] The silicone composition represented by the formula:
##STR00041##
wherein:
[0165] R.sup.4 is selected from the group consisting of methyl and
a group represented by the formula:
##STR00042##
[0166] R.sup.3 is a monohydroxy-terminated partial ester
residue;
[0167] m is 10; and
[0168] x is from about 6 to about 110, preferably from about 6 to
about 50.
[0169] R.sup.4 can be a group represented by the formula:
##STR00043##
[0170] wherein R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00044##
[0171] Where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid.
[0172] The mono-hydroxy-terminated partially esterified ester
residue is derived from a mono-hydroxy-terminated partially
esterified alcohol.
[0173] Preferably, the mono-hydroxy-terminated partially esterified
alcohol is derived from di-, tri- or tetra-functional alcohol
represented by the formula:
R.sup.5(OH).sub.n
[0174] wherein:
[0175] R.sup.5 is an n-functional hydrocarbon residue; and
[0176] n is from about 2 to about 8, preferably from 2 to 4.
[0177] Preferably, the di-, tri- or tetra-functional alcohol is
selected from ethylene glycol, propylene glycol, butylene glycol,
polyethylene glycol, neopentyl glycol, polypropylene glycol,
glycerin, trimethylolethane, trimethylolpropane, pentaerythritol,
di-pentaerythritol, tri-pentaerythritol, and a mixture thereof,
most preferably trimethylolpropane.
[0178] Alternatively, the mono-hydroxy-terminated partially
esterified ester is represented by the formula:
(R.sup.7COO).sub.n-1R.sup.6(OH)
wherein:
[0179] R.sup.6 is an (n-1)-functional hydrocarbon residue
group;
[0180] R.sup.7 is a hydrocarbyl group; and
[0181] n is from about 2 to about 4.
[0182] Preferably, the vinyl-terminated carboxylic acid ester of a
partially esterified ester is represented by the formula:
CH.sub.2.dbd.CH--(CH.sub.2).sub.m-2--COOR.sup.6(OOCR.sup.7).sub.n-1
wherein:
[0183] R.sup.6 is an (n-1)-functional hydrocarbon residue;
[0184] R.sup.7 is a hydrocarbyl group;
[0185] m is about 5 to about 22; and
[0186] n is from about 2 to about 8, preferably from about 2 to
about 4.
[0187] Preferably, the vinyl-terminated carboxylic acid ester of a
partially esterified ester is formed by reacting a
mono-hydroxy-terminated partially esterified ester with either an
olefinic acid, methyl ester or anhydride.
[0188] Preferably, the vinyl-terminated carboxylic acid ester of a
partially esterified ester is hydrosilated with a hydride
terminated polysiloxane represented by the formula:
##STR00045##
wherein:
[0189] R.sup.1 and R.sup.2 are independently selected from methyl,
ethyl and phenyl; and
[0190] x is from about 0 to about 1000.
Alternatively, the hydride can be located internally.
[0191] Preferably, the vinyl-terminated carboxylic acid ester of a
partially esterified ester is represented by the following
formula:
CH.sub.2.dbd.CH--(CH.sub.2).sub.m-2--COOR.sup.3
[0192] R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group.
##STR00046##
[0193] where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid; and
[0194] m is from about 5 to about 22.
[0195] The silicone ester compound formed according to the
preferred method has the formula:
##STR00047##
wherein:
[0196] R.sup.1 and R.sup.2 are independently selected from methyl,
ethyl and phenyl;
[0197] R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00048##
[0198] where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid;
[0199] m is from about 5 to about 22; and
[0200] x is from about 0 to about 1000.
[0201] Preferably, the silicone hydride precursor is represented by
the formula:
##STR00049##
wherein:
[0202] R.sup.1 and R.sup.2 are independently selected from methyl,
ethyl and phenyl; and
[0203] x is from about 0 to about 1000.
Alternatively, the hydride can be located internally.
[0204] In a preferred embodiment, the silicone hydride precursor
has one or more block polymers or block copolymers in the backbone.
For example, the backbone group represented by the formula:
##STR00050##
can have one or more of the same or different block copolymers and
the silicone ester compound can be represented by the formula:
##STR00051##
wherein R.sup.4 is selected from alkyl and a group represented by
the formula:
##STR00052##
[0205] a is an integer from 1 to 20;
[0206] b is an integer from 0 to 200;
[0207] R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00053##
[0208] where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid; and
[0209] m is an integer from about 5 to about 22;
with the proviso that all R.sup.4 groups are not alkyl.
[0210] The hydride terminated polysiloxane and vinyl terminated
carboxylic ester of a partially esterified ester are heated to
80-120.degree. C. and a platinum hydrosilation catalyst such as
hloroplatinic acid or any other platinum catalyst familiar to those
skilled in the art is added up to about 100 ppm. Optionally a
solvent such as toluene, xylene, IPA or any other solvent that is
familiar to those skilled in the art can be used. The reaction is
heated at 80-120.degree. C. until all silicone hydride is consumed,
which usually takes about 2-8 hours. If a solvent is used, it is
then stripped under vacuum.
[0211] Esters have been used for a number of years for a variety of
applications including lubricants. In most cases, the esters are
fully esterified. For esters of polyhydric alcohols, nearly all the
hydroxyl groups have been reacted with acids so that the hydroxyl
number is generally less than about 5 (<.about.5).
[0212] By limiting the extent of the reaction, for example, by
shortening the reaction time or starving the reaction mixture of at
least one of the reactants, partial esters can be created. Polyol
ester compositions having unconverted hydroxyl groups have been
used as lubricant base stocks. Their preparation and uses have been
described in U.S. Pat. No. 5,698,502.
[0213] Partially reacted esters provide the desired reactive
intermediate functional groups for hydrosilation and branching. For
example, certain polyhydric alcohols, such as, pentaerythritol,
provide a neopentyl carbon with a CH.sub.2OH group attached.
Reacting an acid to one, two, or three of these functional groups
provides the partial ester.
[0214] Partially esterified esters having only one free hydroxyl
group are preferred, preferably about 0.7 hydroxyl groups. This
reduces opportunities for cross-linking during the hydrosilation
process. An example of a preferred hydrosilation process is set
forth in U.S. Pat. No. 5,561,231, which is incorporated herein by
reference in its entirety.
[0215] Other multifunctional alcohols include trimethylolpropane,
pentaerythritols, neopentyl glycol, sorbitol and mixtures
thereof.
[0216] In the practice of the invention, the alcohols are allowed
to react with carboxylic acids to produce partially or fully
esterified esters or mixtures of partially and fully esterified
esters.
[0217] The acid can be a monocarboxylic acid, such as, octanoic
acid, and can vary in chain length to provide the desired branching
in the final product. The acid can also be a multi-functional acid.
Examples of such multi-functional acids include adipic acid.
[0218] Silicone ester compounds with a range of molecular weights
can be prepared by reacting the ester created from esterification
of a vinyl containing molecule with an esterified ester with a
silicone backbone. The resulting compounds have unique properties
that make them useful in a number of applications.
[0219] The present disclosure further contemplates the use of more
complex esters, such as, complex esters resulting from the reaction
of polyhydric alcohol with a multifunctional acid followed by
further reaction with a monofunctional alcohol to produce a
partially esterified ester.
[0220] The partially esterified esters can be reacted with an
olefinic acid, such as, undecylenic acid and thereafter
hydrosilated, for example, with a hydride terminated
polysiloxane.
[0221] The number of Si atoms in the above molecule represents a
preferred range. However, the number of Si atoms could be higher,
by way of examples only, as high as a 1000.
[0222] Monohydroxy-terminated partial ester can be represented by
the formula:
R.sup.3--OH
[0223] wherein R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00054##
[0224] where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid.
[0225] Thus, the present disclosure provides a silicone ester
compound with esterified groups represented by the formula:
##STR00055##
wherein:
[0226] R.sup.1 and R.sup.2 are independently selected from methyl,
ethyl and phenyl;
[0227] R.sup.4 is selected from methyl, ethyl, phenyl and a group
represented by the formula:
##STR00056##
[0228] R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group.
##STR00057##
[0229] where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid;
[0230] m is an integer from 5 to 22; and
[0231] x is an integer from about 0 to about 1000.
[0232] In a preferred embodiment of the above silicone fluids,
R.sup.1 and R.sup.2 are both methyl groups, m is from 10 to 14 and,
more preferably, m is 10, x is from about 6 to about 110 and, more
preferably, x is from about 6 to about 50.
[0233] Typically, R.sup.3 is a mono-hydroxy-terminated partially
esterified ester residue which is derived from a
mono-hydroxy-terminated partially esterified alcohol.
[0234] The mono-hydroxy-terminated partially esterified alcohol is
preferably derived from di-, tri- or tetra-functional alcohol
represented by the formula:
R.sup.5(OH).sub.n
[0235] wherein:
[0236] R.sup.5 is an n-functional hydrocarbon residue; and
[0237] n is from 2 to 8, preferably from 2 to 4.
[0238] Preferably, the di-, tri- or tetra-functional alcohol is
ethylene glycol, propylene glycol, butylene glycol, polyethylene
glycol, neopentyl glycol, polypropylene glycol, glycerin,
trimethylolethane, trimethylolpropane, pentaerythritol,
di-pentaerythritol, tri-pentaerythritol, or a mixture thereof
Preferably, the di, tri- or tetra-functional alcohol is
trimethylolpropane.
[0239] The R4 group can be either a methyl group or it can be a
group represented by the formula:
##STR00058##
[0240] whereinR.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00059##
where in this case the two esterified groups on the molecule have
been reacted with heptanoic acid;
[0241] m is an integer from 5 to 22; and
[0242] x is an integer from about 0 to about 1000.
[0243] In a more preferred embodiment, the silicone ester compound
is represented by the formula:
##STR00060##
wherein:
[0244] R.sup.4 is a methyl or a group represented by the
formula:
##STR00061##
[0245] R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00062##
[0246] where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid;
[0247] m is 10; and
[0248] x is from about 6 to about 110.
[0249] More preferably, x is from about 6 to about 50, R.sup.3 is a
mono-hydroxy-terminated partially esterified ester residue derived
from a mono-hydroxy-terminated partially esterified alcohol which,
in turn, is derived from di-, tri- or tetra-functional alcohol
represented by the formula:
R.sup.5(OH).sub.n
[0250] wherein:
[0251] R.sup.5 is an n-functional hydrocarbon residue; and
[0252] n is an integer from 2 to 8, preferably from 2 to 4.
[0253] Examples of the di-, tri- or tetra-functional alcohols
include ethylene glycol, propylene glycol, butylene glycol,
polyethylene glycol, neopentyl glycol, polypropylene glycol,
glycerin, trimethylolethane, trimethylolpropane, pentaerythritol,
di-pentaerythritol, tri-pentaerythritol, and a mixture thereof.
[0254] Trimethylolpropane is preferred.
[0255] The mono-hydroxy-terminated partially esterified ester can
be represented by the formula:
(R.sup.7COO).sub.n-1R.sup.6(OH)
wherein:
[0256] R.sup.6 is an (n-1)-functional hydrocarb residue group;
[0257] R.sup.7 is a hydrocarbyl group; and
[0258] n is an integer from 2 to 8, preferably from 2 to 4.
[0259] The present disclosure further provides a process for
preparing a silicone ester compound including the step of
contacting:
[0260] (i) a hydride terminated polysiloxane represented by the
formula:
##STR00063##
and
[0261] (ii) a vinyl-terminated carboxylic acid ester of partially
esterified ester represented by the formula:
CH.sub.2.dbd.CH--(CH.sub.2).sub.m-2--COOR.sup.3
at a temperature and for a period of time sufficient to produce a
silicone ester compound represented by the formula:
##STR00064##
wherein:
[0262] R.sup.1 and R.sup.2 are independently selected from methyl,
ethyl and phenyl;
[0263] R.sup.3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group
##STR00065##
[0264] where in this case the two esterified groups on the molecule
have been reacted with heptanoic acid;
[0265] m is an integer from 5 to 22; and
[0266] x is an integer from about 0 to about 1000.
[0267] In a preferred embodiment of the process described above,
R.sup.1 and R.sup.2 are both methyl groups, m is from 10 to 14,
more preferably m is 10, x is from about 6 to about 110, and more
preferably, x is from about 6 to about 50.
[0268] Preferably, R3 is derived from a partially esterified ester
residue, e.g., for a partially esterified trimetholpropane shown
here, the residue is the structure without the remaining free
hydroxyl group.
##STR00066##
[0269] where in this case the two esterified groups on the molecule
have been reacted with an acid, derived from a
mono-hydroxy-terminated partially esterified alcohol derived from
di-, tri- or tetra-functional alcohol represented by the
formula:
R.sup.5(OH).sub.n
[0270] wherein:
[0271] R.sup.5 is an n-functional hydrocarbon residue; and
[0272] n is an integer from 2 to 8, preferably from 2 to 4.
[0273] The di-, tri- or tetra-functional alcohol can be ethylene
glycol, propylene glycol, butylene glycol, polyethylene glycol,
neopentyl glycol polypropylene glycol, glycerin, trimethylolethane,
trimethylolpropane, pentaerythritol, di-pentaerythritol,
tri-pentaerythritol, or a mixture thereof.
[0274] Trimethylolpropane is preferred.
[0275] The mono-hydroxy-terminated partially esterified ester is
represented by the formula:
(R.sup.7COO).sub.n-1R.sup.6(OH)
wherein:
[0276] R.sup.6 is an (n-1)-functional hydrocarbon residue
group;
[0277] R.sup.7 is a hydrocarbyl group; and
[0278] n is from 2 to 8, preferably from 2 to 4.
[0279] The vinyl-terminated carboxylic acid ester of partially
esterified ester can be represented by the formula:
CH.sub.2.dbd.CH--(CH.sub.2).sub.m-2--COOR.sup.6(OOCR.sup.7).sub.n-1
wherein:
[0280] R.sup.6 is an (n-1)-functional hydrocarbon residue
group;
[0281] R.sup.7 is a hydrocarbyl group;
[0282] m is an integer 5 to 22; and
[0283] n is an integer from 2 to 8, preferably from 2 to 4.
[0284] It is possible to have a much more complex structure at one
or more positions of the silicone fluid. For example, the ester
intermediate can have more than one free hydroxyl groups present.
In this case, cross-linking via the ester groups is possible. Thus,
each free hydroxyl group could react with the olefinic acid and the
resulting product could then react with two silicone compounds.
[0285] The process for preparing a silicone fluid includes the step
of contacting the hydride terminated polysiloxane and the
vinyl-terminated carboxylic acid ester of partially esterified
ester described herein. The hydride terminated polysiloxane and
vinyl terminated carboxylic ester of a partially esterified ester
are heated to 80-120.degree. C. and a platinum hydrosilation
catalyst such as chloroplatinic acid or any other platinum catalyst
familiar to those skilled in the art is added at 5 to 100 ppm.
Optionally, a solvent such as toluene, xylene, IPA or any other
solvent that is familiar to those skilled in the art can be used.
The reaction is heated at 80-120.degree. C. until all silicone
hydride is consumed, which usually takes about 2-8 hours. If a
solvent is used, it is then stripped under vacuum.
[0286] A functionalized ester was prepared by hydrosilating
[0287] (1) an ester of undecylenic acid reacted with a partial
ester of trimethylolpropane with a linear octanoic/decanoic acid
blend with a
[0288] (2) with a hydride terminated polysiloxane represented by
the following formula
##STR00067##
wherein: R.sup.1 and R.sup.2 are methyl groups and x is
approximately 45. The fluid viscosities and viscosity index (VI) of
the product and of the functionalized esters are compared to the
values that would be observed for the free ester and the hydride
terminated polysiloxane in the following table:
TABLE-US-00001 Material C8/10 based Calculated Silicone
Trimethylol- functionalized functionalized Di-45 propane Di-45
w/Ester Di-45 ester ester{3} Free Ester 100 18.8 0 0 content, %
Kinematic Vis, cSt {1} & {2} 40.degree. C. 19 186 315.6 38.3
100.degree. C. 4.3 51 90.5 16.3 VI 136 323 351 437 {1} ASTM method
for kinematic vis is D445 {2} ASTM method for VI is D2270 {3} The
results for the pure fractions were calculated using this
logarithmic blending rule: Ln (Blend Viscosity) = x1 * ln
(viscosity1) + x2 * ln (viscosity2) where x = weight fraction of
each component viscosity = kinematic viscosity of each
component
[0289] In this equation, the viscosity of the blend {labeled
functionalized Di-45 with ester can be measured directly. The
properties of the free ester can be measured on a fully esterified
product which would be produced separately. The weight fraction of
the free ester can be determined by either gas chromatography or
thermal gravimetric analyses (TGA) and the amount of functionalized
ester can be determined by difference. As a result, all values in
the equation are known except viscosity 2 (the viscosity of the
functionalized ester) which can then be determined by direct
substitution.
[0290] Selected silicone-containing esters derived from this group
were evaluated for their dispersion properties. The solid selected
for dispersion was a zinc oxide product coated with triethyl
caprylyl silane known commercially as Z-Cote HP1, manufactured and
sold by BASF. It is a potent sunscreen product used in
concentrations of about 2 to about 10% usually in oil-in-water
formulations. The test utilized to measure the dispersion
effectiveness of a molecule is as follows: [0291] Test
pigments/particulates are thoroughly dispersed using a Silverson
Mixer at 9000 rpm in 15 gram increments in the selected emollient.
[0292] After each addition the Brookfield viscosity at ambient
temperature was determined. [0293] Additions of 15 grams are
continued until the viscosity increases substantially; usually 10
to 100-fold (approximately 10,000 cP+).
[0294] The test significance is as follows: [0295] Evaluates the
wetting efficiency of an emollient. [0296] The lower the dispersion
viscosity increase compared to the emollient's neat viscosity, the
better the wetting of the pigment. [0297] Low viscosity increase is
associated with good wetting, i.e., uniform spreading of the
emollient, little or no air entrainment, and no agglomeration
(i.e., small particle size). [0298] High viscosity increase is
associated with agglomeration.
[0299] An arbitrary rating system has been established to compare
the efficacy and is shown graphically in FIG. 1 along with the data
generated for the silicone esters in FIGS. 2 and 3.
[0300] The data set forth in FIGS. 2 and 3 clearly demonstrate that
the addition of the silicone moieties in Exxon Di-10, Di-45, Di-100
and Exxon D2 and D10 results in substantially improved dispersion
properties versus the non-silicone products MCP 2262 and PureSyn
3E20. Additionally, substantial improvement over the
polyalphaolefin PureSyn 6 is observed. It is anticipated that the
advantage associated with these results translates into excellent
potential for use of these silicone products in sunscreen,
antiperspirant/deodorant and facial makeup formulations at lower
concentrations, i.e., 1% to 15%, because of their superior
dispersing properties.
[0301] The tables below demonstrate the unique refractive index,
surface tension and viscosity properties of the use of the silicone
esters of the present disclosure versus conventional PAO's,
etc.
TABLE-US-00002 TABLE 1 Property Ester PAO Exxon Di-45 Exxon D10
Silicone Refractive 1.45 1.45 1.43 1.44 1.40 Index @25.degree. C.
Surface 30 29-31 22.3 22.7 21.2 Tension @25.degree. C., dynes/cm
Viscosity 34 900 170 290 500 @25.degree. C., cSt
TABLE-US-00003 TABLE 2 SpectraSyn GR II EHC Wt % Ester SpectraSyn4
40 45 Dow 200-5 cSt Dow 200-200 cSt C8C10 TMP 100 S S S H H Exxon
Di-10 <2 S Vsl H S S H Exxon Di-45 <2 S S S S H Exxon Di-100
<2 Vls H H S S Vsl H Exxon D2 <2 S S S I H Exxon D10 <2 S
S S S H
[0302] In Table 1 two silicone esters (i.e., Exxon Di-45 and Exxon
D10) were compared to an ester, a polyalphaolefin, and a silicone,
wherein the following properties were compared:
[0303] 1. Refractive Index: Ester addition to Silicone backbone
will increase refractive index from 1.40 to Ester and PAO range.
This is greatly beneficial in personal care formulation, since
increase in even the 2nd decimal number is significant.
[0304] 2. Surface Tension: Silicone is known for its characteristic
surface tension to be used in the formulation. Ester and PAO can
hardly compete. It is shown here that by addition of an ester on a
silicone backbone, the silicone ester of the present disclosure,
will have the same great surface tension character as silicone, but
with added compatibility benefit with other fluids that silicone
alone is lacking.
[0305] 3. Viscosity: As a reference on thickness of the fluids.
[0306] Table 2 shows the beneficial compatibility of silicone ester
fluids with other typical reference fluids, which is unique and can
be tailored by molecular design. -10 wt % fluid in left column is
mixed with reference fluids on the top row for solubility test.
[0307] C8C10TMP is the ester attached to the silicone backbone (in
left column along with other silicone ester fluids containing
greater than 2% C8C10TMP ester). SpectraSyn 4 is a low viscosity
short chain polyalphaolefin hydrocarbon. SpectraSyn 40 is a high
viscosity long chain polyalphaolefin hydrocarbon. Gr II EHC 45 is a
typical mineral oil hydrocarbon. Dow 200-5 cSt--is a low viscosity
short chain silicone fluid. Dow 200-200 cSt--is a high viscosity
long chain silicone fluid.
[0308] Typically, organic fluids are not soluble in silicone
fluids. This table 2 shows the following:
[0309] Addition of an ester on a silicone backbone can change its
compatibility with all hydrocarbons;
[0310] The same silicone ester molecule can be compatible with
silicone fluids; and
[0311] Compatibility can be tailored by tailoring the molecule by
dictating the silicone backbone and the ester type and ratio.
Formulations
[0312] 1. 2-in-1 Shampoo with Silicone Esters
Description:
[0313] This 2-in-1 shampoo provides luxurious and lubricious foam
while delivering excellent cleaning and conditioning without
residual buildup.
TABLE-US-00004 Phase Ingredient INCI Designation Wt % A Deionized
Water Water 53.04 A Disodium EDTA Disodium EDTA 0.20 A Carbopol
Ultrez 20 Carbomer 0.30 A Mackadet APB Commercial Package 45.00
from McIntyre B Silicone Ester 1.00 C Belle Aire Tango Fragrance
0.05 Mango 23008 D Kathon CG Methylchloroisothiazolinone 0.05 (and)
Methylisothiazolinone E NaOH (20% Soln.) Sodium Hydroxide 0.00 E
Citric Acid (20% Soln.) Citric Acid 0.00 F Sodium Chloride Sodium
Chloride 0.11 Total 100.00
Blending Procedure
[0314] 1. Dissolve Disodium EDTA in water and add Mackadet APB,
heat to 60.degree. C.
[0315] 2. Mix phase B and heat to 60.degree. C. and mix until
uniform
[0316] 3. Add phase B to phase C and cool to 40.degree. C., Add
phase E to the A Batch
[0317] 4. Add phase D
[0318] 5. Adjust pH to 6.5-7.0 with phase E
[0319] 6. Adjust viscosity to 6,000-12,000 cP with ammonium
chloride solution
2. Medicated Lip Balm with Silicone Esters
TABLE-US-00005 Phase Ingredient INCI Designation Wt % A Ultrapure
Petrolatum Petrolatum 93.30 A Silicone Esters 3.00 B Camphor
Camphor 2.50 C Menthol Menthol 0.50 D Flavor MF 102079 Flavor 0.50
E Vitamin E Acetate Tocopheryl Acetate 0.10 F D&C Green # 6
(0.1% in Green 6 0.10 oil) Total 100.00
Blending Procedure
[0320] 1. Heat phase A to 70.degree. C.
[0321] 2. Cool to 60.degree. C. and add remaining ingredients.
[0322] 3. Pour at 55.degree. C.
3. Moisturizing Lotion with Silicone Ester
TABLE-US-00006 Phase Ingredient INCI Designation Wt % A Deionized
Water Water 62.80 A Carbopol 980 (2% Soln) Carbomer 20.00 A
Na.sub.2EDTA Disodium EDTA 0.10 A Propylene Glycol Propylene Glycol
2.00 B Promulgen D Cetearyl Alcohol 2.00 (and) Ceteareth-20 B
Silicone Ester 10.00 B Arlacel 165 Glyceryl Stearate (and) 1.50
PEG-100 Stearate C Triethanolamine 99% to pH Triethanolamine 0.60
6.5-7.0 D Germaben II Propylene Glycol 1.00 (and) Diazolidinyl Urea
(and) Methylparaben (and) Propylparaben Total 100.00
Blending Procedure
[0323] 1. Heat phase A to 70.degree. C.
[0324] 2. Heat phase B to 70.degree. C.
[0325] 3. Add phase B to phase A
[0326] 4. Add phase C. Cool to 50.degree. C. and add phase D.
4. Organic Sunscreen Spray with PureSyn 2,4, and Silicone
Esters
[0327] Description:
[0328] PureSyn 2, 4, silicone esters are used in this .about.SPF 30
spray that has a broad spectrum UVA/UVB protection. The combination
of a fast, a medium spreading PureSyn plus a slow spreading
silicone ester product provides an improved elegant cascading
emollient feel.
TABLE-US-00007 Phase Ingredient INCI Designation Wt % A Ceralution
C Water (and) Caprylic/Capric 12.00 Triglyceride (and) Glycerin
(and) Ceteareth-25 (and) Sodium Dicocoylethylenediamine PEG-15
Sulfate (and) Sodium Lauroyl Lactylate (and) Behenyl Alcohol (and)
Glyceryl Stearate Citrate (and) Xanthan Gum B Finsolv TN C12-15
Alkyl Benzoate 3.50 B Mandorwax Hydrogenated Sweet Almond Oil 0.50
(and) Hydrogenated Sweet Almond Oil Unsaponifiables (and) Prunus
Amygdalus Dulcis (Sweet Almond) Oil Unsaponifiables B Uvinul MC 80
Ethylhexyl Methoxycinnamate 7.50 (Octinoxate) B Uvinul M 40
Benzophenone-3 (Oxybenzone) 5.00 B PureSyn 2 Hydrogenated C6-14
Olefin 1.00 Polymers B PureSyn 4 Hydrogenated C6-14 Olefin 1.00
Polymers B Silicone Ester 1.00 B Dow Corning Cyclopentasiloxane
1.00 245 Fluid B Escalol 587 Ethylhexyl Salicylate (Octisalate)
5.00 B Vitamin E Tocopheryl Acetate 0.10 Acetate B Uvinul N 539 T
Octocrylene 9.00 C Deionized Water Water (Aqua) 49.80 C LaraCare
A200 Galactoarabinan 2.00 C Avicel PC-611 Microcrystalline
Cellulose (and) 0.50 Cellulose Gum C Disodium EDTA Disodium EDTA
0.10 C Germaben II Propylene Glycol (and) Diazolidinyl 1.00 Urea
(and) Methyl Paraben (and) Propylparaben Total 100.00
Blending Procedure:
[0329] 1. Add phase A to a beaker large enough to accommodate the
entire batch, heat with mixing to 85.degree. C.
[0330] 2. In a separate vessel combine phase B ingredients and heat
to 85.degree. C. with mixing. Very slowly add phase B to phase A
with rapid mixing maintaining 85.degree. C. Homogenize for 3
minutes at 4,500-5,000 rpm.
[0331] 3. Heat the phase C water to 50.degree. C. and disperse the
Laracare A200 into the water and mix well. Disperse the Avicel
PC-611 into the water as well and mix until hydrated (batch will
become uniform in consistency, minimum time=10 minutes). Add
Disodium EDTA to this mixture and mix for an additional 15 minutes.
Add this premixed phase C to the batch with mixing.
[0332] 4. Cool entire batch to 40.degree. C. to room temperature,
Add phase D to the batch with mixing. homogenize for 2 minutes at
5,000 rpm and package.
5. Antiperspirant Roll-on with Silicone Esters
TABLE-US-00008 ANTIPERSPIRANT ROLL-ON with Silicone Esters A B C D
Phase Ingredient INCI Designation Wt % Wt % Wt % Wt % A DC 345
Fluid Cyclomethicone 51.2 31.2 26.2 16.2 A Bentone Bel VS-5
Cyclomethicone 12.5 12.5 12.5 12.5 PC (and) Quaternium-18 Hectorite
(and) Propylene Carbonate B Silicone Ester 10.0 30.0 35.0 45.0 C
Rezal 36GP Aluminum 20.0 20.0 20.0 20.0 Zirconium Tetra-
chlorohydrex- GLY C Talc 127 Talc 2.0 2.0 2.0 2.0 D Dow Corning 190
PPG/PEG-18/18 4.0 4.0 4.0 4.0 Surfactant Dimethicone D Fragrance
Fragrance 0.3 0.3 0.3 0.3 Total 100.0 100.0 100.0 100.0
[0333] Blending Procedure
[0334] 1. Using the Silverson at 3000 rpm with large head mix phase
A (3 min.)
[0335] 2. Add phases B & C
[0336] 3. Mix phase D together and add to batch
[0337] 4. Mix on Silverson until uniform
TABLE-US-00009 REDUCED RESIDUE ANTIPERSPIRANT STICK with Silicone
Esters A B C Phase Ingredient INCI Designation Wt % Wt % Wt % A
Silicone Ester 10.0 25.0 53.5 A Hydrogenated Hydrogenated Castor
Oil 2.5 2.5 2.5 Castor Oil A PEG-8 Distearate PEG-8 Distearate 1.0
1.0 1.0 A Stearyl Alcohol Stearyl Alcohol 18.0 18.0 18.0 B Dow
Corning 345 Cyclomethicone 43.5 28.5 Fluid C Cabosil M-5 Silica 0.5
0.5 0.5 D REACH AZP 908 Aluminum Zirconium 24.0 24.0 24.0 SUF
Tetrachlorohydrex GLY E Fragrance Fragrance 0.5 0.5 0.5 Total 100.0
100.0 100.0
[0338] Blending Procedure
[0339] 1. Mix and heat ingredients of phase A to 85.degree. C. or
until clear, Cool to 70.degree. C.
[0340] 2. Heat phase B to 70.degree. C., add to phase A and mix
well (except Formulation C)
[0341] 3. Slowly add phases C and D while maintaining 70.degree.
C.
[0342] 4. Mix well until homogeneous, cool to 56-58.degree. C. and
add phase E
[0343] 5. Mix well and pour into stick containers
6. Reduced Residue Antiperspirant Stick with Silicone Esters
TABLE-US-00010 REDUCED RESIDUE ANTIPERSPIRANT STICK with Silicone
Esters A B Phase Ingredient INCI Designation Wt % Wt % C A Silicone
Ester 20.0 10.0 5 A Hydrogenated Hydrogenated 2.5 2.5 2.5 Castor
Oil A PEG-8 Distearate PEG-8 Distearate 1.0 1.0 1.0 A Stearyl
Alcohol Stearyl Alcohol 18.0 18.0 18.0 B Dow Corning 345 Fluid
Cyclomethicone 33.5 43.5 48.5 C Cabosil M-5 Silica 0.5 0.5 0.5 D
REACH AZP 908 SUF Aluminum 24.0 24.0 24.0 Zirconium Tetrachloro-
hydrex GLY E Fragrance Fragrance 0.5 0.5 0.5 Total 100.0 100.0
100.0
[0344] Blending Procedure
[0345] 1. Mix and heat ingredients of phase A to 85.degree. C. or
until clear,Cool to 70.degree. C.
[0346] 2. Heat phase B to 70.degree. C.,add to phase A and mix well
(except Formulation C)
[0347] 3 Slowly add phases C and D while maintaining 70.degree.
C.
[0348] 4. Mix well until homogeneous, cool to 56-58.degree. C. and
add phase E
[0349] 5. Mix well and pour into stick containers
[0350] The present disclosure has been described with particular
reference to the preferred embodiments. It should be understood
that the foregoing descriptions and examples are only illustrative
of the invention. Various alternatives and modifications thereof
can be devised by those skilled in the art without departing from
the spirit and scope of the present disclosure. Accordingly, the
present disclosure is intended to embrace all such alternatives,
modifications, and variations that fall within the scope of the
appended claims.
* * * * *